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Results for “Phase Transformation”

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All sources NASA NTRS DOE OSTI

DOE OSTI2017

Magnetic phase transformations and magnetotransport phenomena in La{sub 0.7}Sr{sub 0.3}Mn{sub 1–} {sub x}Co{sub x}O{sub 3} perovskite compounds

The compositions La{sub 0.7}Sr{sub 0.3}Mn{sub 1–} {sub x}Co{sub x}O{sub 3} (0.13 ≤ x ≤ 1) are studied by neutron diffraction, magnetometry, and measuring the magnetotransport properties. The substitution of cobalt ions for manganese ions is shown to decrease the magnetization and the Curie temperature from 270 K (x = 0.13) to 140 K (x = 0.33). As the cobalt ion content increases to x = 0.5, the Curie temperature increases to 190 K, the magnetization decreases, and the electrical resistivity increases. At x > 0.5, the temperature of transition into a paramagnetic state decreases to 68 K (x = 0.8) and then again increases to 225 K for the La{sub 0.7}Sr{sub 0.3}CoO{sub 3} composition. The magnetoresistive effect in the range 0.3 ≤ x ≤ 0.4 reaches 97% and decreases gradually with increasing temperature without anomalies near the Curie point. At x ≤ 0.2, the magnetoresistive effect increases near the Curie temperature. The composition at x = 0.6 is stoichiometric, and no coherent magnetic contribution to neutron scattering is detected. The magnetic properties near x ∼ 0.5 are assumed to be caused by partial ordering of Co{sup 3+} and Mn{sup 4+} ions, and the Co{sup 3+} ions can be in both low- and high-spin states. The magnetic interaction between Co{sup 3+} ions in a high-spin state and Mn{sup 4+} is predominantly ferromagnetic, and the ferromagnetic part of the exchange interactions is close to the ferromagnetic part. These data are used to plot a magnetic La{sub 0.7}Sr{sub 0.3}Mn{sub 1–} {sub x}Co{sub x}O{sub 3} phase diagram.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2014

Phase transformation, improved ferroelectric and magnetic properties of (1 − x) BiFeO{sub 3}–xPb(Zr{sub 0.52}Ti{sub 0.48})O{sub 3} solid solutions

The authors prepared (1 − x)BiFeO{sub 3} – (x)Pb(Zr{sub 0.52}Ti{sub 0.48})O{sub 3} for x ≤ 0.30 by sol-gel method and investigated the material's structures, magnetic and electrical properties. Detailed Rietveld analysis of X-ray diffraction data revealed that the system retains distorted rhombohedral R3c structure for x ≤ 0.10 but transforms to monoclinic (Cc) structure for x > 0.10. Disappearance of some Raman modes corresponding to A1 modes and the decrease in the intensities of the remaining A1 modes with increasing x in the Raman spectra, which is a clear indication of structural modification and symmetry changes brought about by PZT doping. Enhanced magnetization with PZT doping content may be attributed to the gradual change and destruction in the spin cycloid structure of BiFeO{sub 3.} The leakage current density at 3.5 kV/cm was reduced by approximately three orders of magnitude by doping PZT (x = 0.30), compared with BFO ceramics.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2013

Ion-beam-induced magnetic and structural phase transformation of Ni-stabilized face-centered-cubic Fe films on Cu(100)

Metastable face-centered cubic (fcc) Fe/Cu(100) thin films are good candidates for ion-beam magnetic patterning due to their magnetic transformation upon ion-beam irradiation. However, pure fcc Fe films undergo spontaneous transformation when their thickness exceeds 10 ML. This limit can be extended to approximately 22 ML by deposition of Fe at increased CO background pressures. We show that much thicker films can be grown by alloying with Ni for stabilizing the fcc γ phase. The amount of Ni necessary to stabilize nonmagnetic, transformable fcc Fe films in dependence on the residual background pressure during the deposition is determined and a phase diagram revealing the transformable region is presented.

36 MATERIALS SCIENCE↗

DOE OSTI2018

Equation of state, phase stability, and phase transformations of uranium-6 wt.% niobium under high pressure and temperature

In-situ time-of-flight neutron diffraction experiments were conducted on the uranium-niobium alloy with 6 wt. % Nb (U–6Nb) at pressures up to 4.7 GPa and temperatures up to 1073 K. Upon static compression at room temperature, the monoclinic structure of U–6Nb (α" U–6Nb) remains stable up to the highest experimental pressure. Based on the pressure-volume measurements at room temperature, the least-squares fit using the finite-strain equation of state (EOS) yields an isothermal bulk modulus of B 0 = 127±2 GPa for the α"-phase of U–6Nb. The calculated zero-pressure bulk sound speed from this EOS is 2.706±0.022 km/s, which is in good agreement with the linear extrapolation of the previous Hugoniot data above 12 GPa for α" U–6Nb, indicating that the dynamic response under those shock-loading conditions is consistent with the stabilization of the initial monoclinic phase of U-6Nb. Upon heating at ambient and high pressures, the metastable α" U–6Nb exhibits complex transformation paths leading to the diffusional phase decomposition, which are sensitive to applied pressure, stress state, and temperature-time path. These findings provide new insight into the behavior of atypical systems such as U-Nb and suggest that the different U-Nb phases are separated by rather small energies and hence highly sensitive to compositional, thermal, and mechanical perturbations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2015

Phase transformations during HLnTiO{sub 4} (Ln=La, Nd) thermolysis and photocatalytic activity of obtained compounds

Layered HLnTiO{sub 4} (Ln=La, Nd) compounds belonging to Ruddlesden–Popper phases were found to form partially hydrated compounds Ln{sub 2}Ti{sub 2}O{sub 7}·xH{sub 2}O during thermal dehydration as well as defect oxides Ln{sub 2}□Ti{sub 2}O{sub 7} as final products. Further heating of metastable defect Ln{sub 2}□Ti{sub 2}O{sub 7} substances leads to the formation of pyrochlore-type oxides Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}, with subsequent transformation under higher temperatures to stable layered 110-type perovskites Ln{sub 2}Ti{sub 2}O{sub 7}. The occurring structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO{sub 4}<Ln{sub 2}Ti{sub 2}O{sub 7}·yH{sub 2}O<Ln{sub 2}□Ti{sub 2}O{sub 7}<Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}<Ln{sub 2}Ti{sub 2}O{sub 7} in the reaction of hydrogen evolution from aqueous isopropanol solution. - Graphical abstract: Layered HLnTiO{sub 4} (Ln=La, Nd) compounds form partially hydrated Ln{sub 2}Ti{sub 2}O{sub 7}·xH{sub 2}O compounds during thermal dehydration, further heating results to the formation to defect oxides Ln{sub 2}□Ti{sub 2}O{sub 7}, pyrochlor-type oxides Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}, with subsequent transformation to layered 110-type perovskites Ln{sub 2}Ti{sub 2}O{sub 7}. Structure transformations lead to an increase of photocatalytic activity in the order of HLnTiO{sub 4}<Ln{sub 2}Ti{sub 2}O{sub 7}·yH{sub 2}O<Ln{sub 2}□Ti{sub 2}O{sub 7}<Ln{sub 2}Ti{sub 2}O{sub 7} {sub (p)}<Ln{sub 2}Ti{sub 2}O{sub 7}. - Highlights: • We studied dehydration and further thermolysis of HLnTiO{sub 4} (Ln=La, Nd) compounds. • XRD, STA and solid state IR studies were carried out. • A new series of metastable Ln{sub 2}Ti{sub 2}O{sub 7}·yH{sub 2}O compounds was obtained. • We examined the photocatalytic activity of all obtained compounds. The hydrogen evolution rate increased in the course of the structure changes during thermolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1988

Phase transformations in xerogels of mullite composition

Monophasic and diphasic xerogels have been prepared as precursors for mullite (3Al2O3-2SiO2). Monophasic xerogel was synthesized from tetraethyl orthosilicate and aluminum nitrate nanohydrate and the diphasic xerogel from colloidal suspension of silica and boehmite. The chemical and structural evolutions, as a function of thermal treatment, in these two types of sol-gel derived mullite precursor powders have been characterized by DTA, TGA, X-ray diffraction, SEM and infrared spectroscopy. Monophasic xerogel transforms to an Al-Si spinel from an amorphous structure at approximately 980 C. The spinel then changes into mullite on further heating. Diphasic xerogel forms mullite at approximately 1360 C. The components of the diphasic powder react independently up to the point of mullite formation. The transformation in the monophasic powder occurs rapidly and yields strongly crystalline mullite with no other phases present. The diphasic powder, however, transforms rather slowly and contains remnants of the starting materials (alpha-Al2O3, cristobalite) even after heating at high temperatures for long times (1600 C, 6 hr). The diphasic powder could be sintered to high density but not the monophasic powder in spite of its molecular level homogeneity.

Hyatt, Mark J.↗

NASA NTRS1990

Phase transformations in xerogels of mullite composition

Monophasic and diphasic xerogels have been prepared as precursors for mullite (3Al203-2Si02). Monophasic xerogel was synthesized from tetraethyl orthosilicate and aluminum nitrate nanohydrate and the diphasic xerogel from colloidal suspension of silica and boehmite. The chemical and structural evolutions, as a function of thermal treatment, in these two types of sol-gel derived mullite precursor powders have been characterized by DTA, TGA, X-ray diffraction, SEM and infrared spectroscopy. Monophasic xerogel transforms to an Al-Si spinel from an amorphous structure at approximately 980 C. The spinel then changes into mullite on further heating. Diphasic xerogel forms mullite at approximately 1360 C. The components of the diphasic powder react independently up to the point of mullite formation. The transformation in the monophasic powder occurs rapidly and yields strongly crystalline mullite with no other phases present. The diphasic powder, however, transforms rather slowly and contains remnants of the starting materials (alpha-Al203, cristobalite) even after heating at high temperatures for long times (1600 C, 6 hr). The diphasic powder could be sintered to high density but not the monophasic powder in spite of its molecular level homogeneity.

Hyatt, Mark J.↗

DOE OSTI2024

Phase Composition and Phase Transformation of Additively Manufactured Nickel Alloy 718 AM Bench Artifacts

Additive manufacturing (AM) technologies offer unprecedented design flexibility but are limited by a lack of understanding of the material microstructure formed under their extreme and transient processing conditions and its subsequent transformation during post-build processing. As part of the 2022 AM Bench Challenge, sponsored by the National Institute of Standards and Technology, this study focuses on the phase composition and phase evolution of AM nickel alloy 718, a nickel-based superalloy, to provide benchmark data essential for the validation of computational models for microstructural predictions. Here, we employed high-energy synchrotron X-ray diffraction, in situ synchrotron X-ray scattering, as well as high-resolution transmission electron microscopy for our analyses. The study uncovers critical aspects of the microstructure in its as-built state, its transformation during homogenization, and its phase evolution during subsequent aging heat treatment. Specifically, we identified secondary phases, monitored the dissolution and coarsening of microstructural elements, and observed the formation and stability of γ ’ and γ ” phases. The results provide the rigorous benchmark data required to understand the atomic and microstructural transformations of AM nickel alloy 718, thereby enhancing the reliability and applicability of AM models for predicting phase evolution and mechanical properties.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Intercalation-Induced Topotactic Phase Transformation of Tungsten Disulfide Crystals

Recent research has demonstrated the potential for topological superconductivity, anisotropic Majorana bound states, optical nonlinearity, and enhanced electrochemical activity for transition metal dichalcogenides (TMDs) with a 2M structure. These unique TMD compounds exhibit metastability and, upon heating, undergo a transition to the thermodynamically stable 2H phase. The 2M phase is commonly made at high temperatures using traditional solid-state methods, and this metastability further complicates the growth of large 2M WS 2 crystals. Herein, a novel synthetic method was developed, focusing on a molten salt reaction to synthesize large 2H crystals and then inducing transformation to the 2M phase through intercalation and thermal treatment. The 2H crystals were intercalated via a room-temperature sodium naphthalenide solution, producing a previously unreported Na-intercalated 2H WS 2 phase. Thermal heating was required to facilitate the phase transition to the intercalated 2M crystal structure. This phase transition was studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), electron dispersive X-ray spectroscopy (EDS), and Raman spectroscopy, which confirmed the synthesis of the intercalated 2M phase. Upon deintercalation, crystal and powder samples showed superconductivity with a T c of 8.6–8.7 K, similar to previously reported values. The generality of this process was further demonstrated using alkali metal triethyl borohydride to intercalate 2H WS 2 and produced the desired 2M phase. This novel synthetic method has broad implications for discovering metastable phases in other TMD families and layered materials. Furthermore, separation of the intercalation and phase transition also has the potential to allow for large-scale synthesis of this technologically important phase with greater control over each step of the reaction.

36 MATERIALS SCIENCE↗

NASA NTRS1994

Diagenetic Microcrystalline Opal Varieties from the Monterey Formation, CA: HRTEM Study of Structures and Phase Transformation Mechanisms

Microcrystalline opal varieties form as intermediary precipitates during the diagenetic transformation of biogenically precipitated non-crystalline opal (opal-A) to microquartz. With regard to the Monterey Formation of California, X-ray powder diffraction studies have shown that a decrease in the primary d-spacing of opal-CT toward that of cristobalite occurs with increasing diagenesis. The initial timing of opal-CT/quartz formation and the value of the primary opal-CT d-spacing, are influenced by the sediment. lithology. Transmission electron microscopy methods (CTEM/HRTEM) were used to investigate the structure of the diagenetic phases and establish transformation mechanisms between the varieties of microcrystalline opals in charts and porcelanites from the Monterey Formation. HRTEM images revealed that the most common fibrous varieties of microcrystalline opals contain varying amounts of structural disorder. Finite lamellar units of cristobalite-and tridymite-type. layer sequences were found to be randomly stacked in a direction perpendicular to the fiber axis. Disordered and ordered fibers were found to have coprecipitated within the same radial fiber bundles that formed within the matrix of the Most siliceous samples. HRTEM images, which reveal that the fibers within radial and lepispheric fiber bundles branch non-crystallographically, support an earlier proposal that microspheres in chert grow via a spherulitic growth mechanism. A less common variety of opal-CT was found to be characterized by non-parallel (low-angle) stacking sequences that often contain twinned lamellae. Tabular-shaped crystals of orthorhombic tridymite (PO-2) were also identified in the porcelanite samples. A shift in the primary d-spacing of opal-CT has been interpreted as an indication of solid-state ordering g toward a predominantly cristobalite structure, (opal-C). Domains of opal-C were identified as topotactically-oriented overgrowths on discrete Sections of opal-CT fibers and as lamellar domains within relict opal-CT fibers. These findings indicate that the type of transformation mechanism depends upon the primary structural characteristics of the authigenic opaline. varieties that are in turn influenced by the sediment lithology.

Cady, Sherry L.↗

DOE OSTI2014

Phase transformation of ZnMoO{sub 4} by localized thermal spike

We show that ZnMoO{sub 4} remains in stable phase under thermal annealing up to 1000 °C, whereas it decomposes to ZnO and MoO{sub 3} under transient thermal spike induced by 100 MeV Ag irradiation. The transformation is evidenced by X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). Thin films of ZnMoO{sub 4} were synthesized by thermal evaporation and subsequent annealing in oxygen ambient at 600 °C for 4 h. XRD results show that as the irradiation fluence increases, the peak related to ZnMoO{sub 4} decreases gradually and eventually disappear, whereas peaks related to ZnO grow steadily up to fluence of 3 × 10{sup 12} ions/cm{sup 2} and thereafter remain stable till highest fluence. This indicates that polycrystalline ZnMoO{sub 4} film has transformed to polycrystalline ZnO thin film. The Raman lines related to ZnMoO{sub 4} are observed to have disappeared with increasing irradiation fluence. XPS results show modification in bonding and depletion of Mo from near surface region after the ion irradiation. Cross-sectional transmission electron microscopy result shows the formation of ion track of diameter 12–16 nm. These results demonstrate that ion beam methods provide the means to control phase splitting of ZnMoO{sub 4} to ZnO and MoO{sub 3} within nanometric dimension along the ion track. The observation of phase splitting and Mo loss are explained in the framework of ion beam induced thermal spike formalism.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2018

Phase transformations of HfNbTaTiZr high-entropy alloy at intermediate temperatures

The strong and ductile single-phase body-centered-cubic (BCC) HfNbTaTiZr refractory high-entropy alloy (RHEA) is a potential structural material for high-temperature applications. However, the BCC phase stability in the intermediate temperature range (500-900 degrees C) needs to be better understood to make this alloy applicable to industry. Here, the phase decomposition of the HfNbTaTiZr RHEA is examined at different temperatures (500-1000 degrees C). Additionally, the formation of BCC Ta-Nb-rich and hexagonal-close-packed (HCP) Hf-Zr-rich precipitates are studied as a function of annealing time at 700 degrees C using a combination of atom probe tomography, transmission electron microscopy, and X-ray diffraction. In conclusion, we found that these BCC and HCP precipitates have preferred orientations with the BCC matrix.

36 MATERIALS SCIENCE↗

DOE OSTI2012

In-situ X-ray diffraction study of phase transformations in the Am-O system

In the frame of minor actinides recycling, americium can be transmuted by adding it in UO{sub 2} or (U, Pu)O{sub 2} fuels. Americium oxides exhibiting a higher oxygen potential than U or Pu oxides, its addition alters the fuel properties. To comprehend its influence, a thorough knowledge of the Am-O phase equilibria diagram and of thermal expansion behavior is of main interest. Due to americium scarcity and high radiotoxicity, few experimental reports on this topic are available. Here we present in-situ high-temperature XRD results on the reduction from AmO{sub 2} to Am{sub 2}O{sub 3}. We show that fluorite (Fm-3m) AmO{sub 2} is reduced to cubic (Ia-3) C Prime -type Am{sub 2}O{sub 3+{delta}}, and then into hexagonal (P6{sub 3}/mmc) A-type Am{sub 2}O{sub 3}, which remains stable up to 1840 K. We also demonstrate the transitional existence of the monoclinic (C2/m) B-type Am{sub 2}O{sub 3}. At last, we describe, for the first time, the thermal expansion behavior of the hexagonal Am{sub 2}O{sub 3} between room temperature and 1840 K. - Graphical abstract: Americium dioxide was in situ studied by high-temperature X-ray diffraction. First, fluorite AmO{sub 2} is reduced to cubic C Prime -type Am{sub 2}O{sub 3+{delta}} and then transforms into hexagonal A-type Am{sub 2}O{sub 3}, which remains stable up to 1840 K. Then, we demonstrate the transitional existence of monoclinic B-type Am{sub 2}O{sub 3}. At last, we describe, for the first time, the thermal expansion of A-type Am{sub 2}O{sub 3} between room temperature and 1840 K. This work may contribute to a better understanding of Am oxide behavior. Highlights: Black-Right-Pointing-Pointer We realize an in-situ high-temperature X-ray diffraction study on an AmO{sub 2} sample. Black-Right-Pointing-Pointer Fluorite AmO{sub 2} transforms to cubic Am{sub 2}O{sub 3+{delta}} and then to hexagonal Am{sub 2}O{sub 3}. Black-Right-Pointing-Pointer Little-known monoclinic Am{sub 2}O{sub 3} is observed during the cubic-to-hexagonal transition. Black-Right-Pointing-Pointer Lattice parameter thermal expansion of hexagonal Am{sub 2}O{sub 3} is given up to 1840 K. Black-Right-Pointing-Pointer We give additional data on AmO{sub 2} lattice parameter expansion under self-irradiation.

36 MATERIALS SCIENCE↗

NASA NTRSDate not supplied

Ab Initio Simulations of Martensitic Phase Transformations in NiTi-based High Temperature Ternary Shape Memory Alloys: NiTiHf and NiTiZr

Ab initio simulations of phase stability and martensitic phase transitions are performed for NiTi-based ternary shape memory alloys (SMAs). Specifically, we considered NiTiHf and NiTiZr, which are highly studied for high temperature SMA applications. Previously, we performed investigations of ordered NiTi and related binaries [1,2]. However, similar approaches for chemically disordered compounds present additional difficulties. In this work, special quasi-random structures (SQS) were generated for various compositions, x∈[0,0.5], of Ni0.5Ti(0.5-x)Hfx and Ni0.5Ti(0.5-x)Zrx to capture chemical disorder of off-stoichiometric compounds. Phase stability was evaluated through analysis of finite temperature phonon spectra using temperature dependent effective potential (TDEP) method. Free energies for the cubic B2 phase of NiTiHf and NiTiZr were computed using ab initio thermodynamic integration (AITI) developed previously [1,2]. Free energies for monoclinic B19’ and orthorhombic B33 phases were evaluated via quasi harmonic approximations (QHA). Our results show a critical composition (xc) where the three phases of B2, B19’ and B33 meet, i.e. there is a tri-critical point. For x xc, the transition is between B33 and B2, i.e. it is not a shape memory transition. The approach presented here opens the door to ab initio based predictions of MTT for arbitrary ternary SMAs.

Hessam Malmir↗

DOE OSTI2020

Peculiarities of the phase transformation dynamics in bulk FeRh based alloys from magnetic and structural measurements

We analyze coexistence of antiferromagnetic and ferromagnetic phases in bulk iron-rhodium and its alloys with palladium, Fe 50,4 Rh 49,6 , Fe 49,7 Rh 47,4 Pd 2,9 and Fe 48,3 Rh 46,8 Pd 4,9 , using neutron diffraction, magnetization and scanning Hall probe imaging. Temperature dependencies of the lattice parameters, AFM and FM phase weight fractions, and Fe magnetic moment values were obtained on cooling and heating across the AFM-FM transition. Substantial thermomagnetic hysteresis for the phases’ weight fractions and a relatively narrow one for the unit cell volume has been observed on cooling-heating. Furthermore, a clear dependence of hysteretic behavior on Pd concentration has been traced. Additional direct magnetic measurements of the spatial distribution of the phase transition are acquired using scanning Hall probe microscopy, which reveals the length scale of the phase coexistence and the spatial progression of the transition in the presence of external magnetic field. Also, the magnetic phase diagram has been constructed for a series of Pd-doped FeRh alloys.

36 MATERIALS SCIENCE↗

DOE OSTI2015

Femtosecond laser-induced phase transformations in amorphous Cu{sub 77}Ni{sub 6}Sn{sub 10}P{sub 7} alloy

In this study, the femtosecond laser-induced crystallization of CuNiSnP amorphous ribbons was investigated by utilizing an amplified Ti:sapphire laser system. X-ray diffraction and scanning electronic microscope were applied to examine the phase and morphology changes of the amorphous ribbons. Micromachining without crystallization, surface patterning, and selective crystallization were successfully achieved by changing laser parameters. Obvious crystallization occurred under the condition that the laser fluence was smaller than the ablation threshold, indicating that the structural evolution of the material depends strongly on the laser parameters. Back cooling method was used to inhibit heat accumulation; a reversible transformation between the disordered amorphous and crystalline phases can be achieved by using this method.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2022

Correlative image learning of chemo-mechanics in phase-transforming solids

We report constitutive laws underlie most physical processes in nature. However, learning such equations in heterogeneous solids (for example, due to phase separation) is challenging. One such relationship is between composition and eigenstrain, which governs the chemo-mechanical expansion in solids. Here we developed a generalizable, physically constrained image-learning framework to algorithmically learn the chemo-mechanical constitutive law at the nanoscale from correlative four-dimensional scanning transmission electron microscopy and X-ray spectro-ptychography images. We demonstrated this approach on Li X FePO 4 , a technologically relevant battery positive electrode material. We uncovered the functional form of the composition–eigenstrain relation in this two-phase binary solid across the entire composition range (0 ≤ X ≤ 1), including inside the thermodynamically unstable miscibility gap. The learned relation directly validates Vegard’s law of linear response at the nanoscale. Our physics-constrained data-driven approach directly visualizes the residual strain field (by removing the compositional and coherency strain), which is otherwise impossible to quantify. Heterogeneities in the residual strain arise from misfit dislocations and were independently verified by X-ray diffraction line profile analysis. Our work provides the means to simultaneously quantify chemical expansion, coherency strain and dislocations in battery electrodes, which has implications on rate capabilities and lifetime. Broadly, this work also highlights the potential of integrating correlative microscopy and image learning for extracting material properties and physics.

36 MATERIALS SCIENCE↗

DOE OSTI2023

On Proton Defects and the Phase Transformation of NiO 2

One approach to high-capacity Li-ion battery cathodes is to increase the Ni content. Unfortunately, Ni-rich materials undergo a phase transition and volume collapse at a high state of charge (SOC), which degrades battery performance. At a high SOC, NiO 2 undergoes a phase transition from the O 3 to the O 1 phase. The O 1 phase appears to be more thermodynamically stable than the O 3 phase. However, density functional theory (DFT) often predicts higher stability for O 3 , depending on the DFT approximation. The energy difference between the O 1 and O 3 phases is on the order of 10 meV/atom. Furthermore, we find that proton defects are more stable in the O 1 phase than in the O 3 phase by about 90 meV per proton. Defects in NiO 2 energetically favor the O 3 -O 1 phase transition observed in a high SOC in Li $x$ NiO 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗